7054
P.M. Habib et al. / Tetrahedron 66 (2010) 7050e7056
41.3. MS m/z (relative intensity) 310 (Mþ, 20), 225 (50), 220 (30),
212 (40). HRMS calcd for C17H14N2O4 (Mþ) 310.0954; found:
310.0938.
1H), 5.18 (dd, J¼8.5, 7.5 Hz, 1H), 5.05 (dd, J¼12.5, 7.5 Hz, 1H), 4.93
(dd, J¼12.5, 8.5 Hz, 1H), 3.74 (s, 3H). 13C NMR (100 MHz, CDCl3):
d¼139.3, 137.5, 129.1, 127.4, 127.1, 126.3, 126.0, 121.8, 119.1, 118.7,
112.4, 109.3, 79.1, 41.2, 32.2. MS m/z (relative intensity) 280 (Mþ,
44), 234 (50), 233 (74), 220 (100), 217 (17), 146 (17), 115 (13). HRMS
calcd for C17H16O2N2 (Mþ) 280.1212; found: 280.1213.
4.7.5. 3-(1-(4-Methylphenyl)-2-nitroethyl)-1H-indole (5a). Viscous
liquid. 1H NMR (400 MHz, CDCl3):
d
¼7.91 (s, 1H), 7.40 (d, J¼7.8 Hz,
1H), 7.23e7.01 (m, 7H), 6.84 (s, 1H), 5.09 (dd, J¼8.6, 7.7 Hz, 1H), 4.95
(dd, J¼12.3, 7.7 Hz,1H), 4.83 (dd, J¼12.3, 8.6 Hz,1H), 2.25 (s, 3H). 13C
4.7.12. 2-(2-Methylindol-3-yl)-2-phenyl-1-nitroethane (12a). Solid,
NMR (100 MHz, CDCl3):
d
¼137.3, 136.6, 136.3, 129.7, 127.7, 126.2,
mp 103e105 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼7.76 (s, 1H), 7.34 (d,
122.7,121.7,119.9,119.0,114.5,111.6, 79.8, 41.3, 21.2. MS m/z (relative
intensity) 280 (Mþ, 26), 272 (29), 233 (86), 225 (100), 220 (72), 212
(70). HRMS calcd for C17H16N2O2 (Mþ) 280.1212; found: 280.1208.
J¼7.8 Hz,1H), 7.28e7.23 (m, 4H), 7.20e7.16 (m, 2H), 7.07 (t, J¼7.7 Hz,
1H), 7.00 (m,1H), 5.20e5.13 (m, 2H), 5.10e5.02 (m,1H), 2.26 (s, 3H).
13C NMR (100 MHz, CDCl3):
126.5,120.8,119.3,118.2,110.6,108.2, 78.2, 40.2,11.2. MS m/z (relative
intensity) 280 (Mþ, 62), 234 (49), 220 (100), 146 (49), 115 (8), 77 (8).
HRMS calcd for C17H16O2N2 (Mþ) 280.1212; found: 280.1218.
d
¼139.3, 135.1, 132.8, 128.4, 127.0, 126.7,
4.7.6. 3-(1-(4-Chlorophenyl)-2-nitroethyl)-1H-indole (6a). Solid, mp
99e101 ꢀC.1H NMR (400 MHz, CDCl3):
d
¼8.07 (s,1H), 7.38 (d, J¼7.9 Hz,
1H), 7.33 (d, J¼8.2 Hz,1H), 7.28e7.17 (m, 5H), 7.07 (t, J¼7.5 Hz,1H), 6.96
(d, J¼1.7 Hz, 1H), 5.14 (dd, J¼8.6, 7.4 Hz, 1H), 5.02 (dd, J¼12.5, 7.4 Hz,
4.7.13. 3-(2-Nitro-1-phenylethyl)-2-phenyl-1H-indole (13a). Solid,
1H), 4.88 (dd, J¼12.5, 8.6 Hz,1H). 13C NMR (100 MHz, CDCl3):
d¼137.6,
mp 143e145 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼8.14 (s, 1H), 7.52 (d,
136.2, 133.0, 128.9, 128.8, 125.6, 122.5, 121.4, 119.8, 118.5, 113.3, 111.4,
79.0, 41.0. MS m/z (relative intensity) 302 (Mþ2, 2), 300 (Mþ, 33), 254
(41), 253 (100), 240 (64), 218 (37), 115 (14), 108 (25). HRMS calcd for
C16H13ClN2O2 (Mþ), 300.0666; found: 300.0671.
J¼8.0 Hz, 1H), 7.44e7.19 (m, 12H), 7.11 (t, J¼7.5 Hz, 1H), 5.32 (t,
J¼8.0 Hz, 1H), 5.20e5.09 (m, 2H). 13C NMR (100 MHz, CDCl3):
d
¼140.1, 137.2, 136.3, 132.4, 129.2, 129.1, 129.0, 128.8, 127.7, 127.4,
127.2, 122.7, 120.5, 120.2, 111.6, 109.8, 79.3, 41.0. MS m/z (relative
intensity) 342 (Mþ, 65), 294 (70), 282 (81), 208 (100), 204 (53).
HRMS calcd for C22H18N2O2 (Mþ) 342.1368; found: 342.1363.
4.7.7. 3-(1-(4-Nitrophenyl)-2-nitroethyl)-1H-indole (7a). Solid, mp
145e147 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼8.20 (s, 1H), 8.16 (d,
J¼8.7 Hz, 2H), 7.51 (d, J¼8.6 Hz, 2H), 7.37 (t, J¼7.3 Hz, 2H), 7.25e7.20
(m, 1H), 7.09 (t, J¼7.7 Hz, 1H), 7.04 (d, J¼2.2 Hz, 1H), 5.29 (dd, J¼8.9,
7.0 Hz, 1H), 5.10 (dd, J¼12.8, 7.0 Hz, 1H), 4.98 (dd, J¼12.8, 8.9 Hz, 1H).
4.7.14. 5-Methoxy-3-(2-nitro-1-phenylethyl)-1H-indole (14a). Solid,
mp 116e118 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼7.99 (s, 1H),
7.30e7.16 (m, 6H), 6.92 (d, J¼2.2 Hz, 1H), 6.84 (d, J¼2.2 Hz, 1H), 6.82
(s, 1H), 5.11 (dd, J¼8.4, 7.6 Hz, 1H), 5.00 (dd, J¼12.4, 7.6 Hz, 1H), 4.89
(dd, J¼12.4, 8.4 Hz, 1H), 3.74 (s, 3H). 13C NMR (100 MHz, CDCl3):
13C NMR (100 MHz, CDCl3):
123.3, 121.8, 120.5, 118.7, 113.1, 111.9, 78.9, 41.4. MS m/z (relative in-
tensity) 311 (Mþ, 7), 264 (21), 185 (24), 110 (47), 97 (43), 71 (71), 57
(100). HRMS calcd for C16H13N3O4 (Mþ), 311.0906; found: 311.0901.
d
¼147.5, 146.9, 136.7, 129.0, 125.8, 124.4,
d
¼154.1, 139.1, 131.5, 128.8, 127.7, 127.5, 126.5, 122.2, 113.9, 112.6,
112.1, 100.8, 79.4, 55.8, 41.4. MS m/z (relative intensity) 296 (Mþ,
86), 250 (75), 249 (100), 236 (98). HRMS calcd for C17H16N2O3
296.1161; found: 296.1163.
4.7.8. 3-(1-Naphthalen-2-yl)-2-nitroethyl-1H-indole (8a). Solid, mp
140e142 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼8.05 (s, 1H), 7.76 (m, 4H),
7.45 (d, J¼7.1 Hz, 3H), 7.39 (d, J¼8.5 Hz,1H), 7.31 (d, J¼8.1 Hz,1H), 7.17
(t, J¼7.5 Hz,1H), 7.05e6.99 (m, 2H), 5.33 (t, J¼7.8 Hz,1H), 5.11 (m,1H),
4.7.15. 5-Bromo-3-(2-nitro-1-phenylethyl)-1H-indole (15a). Solid,
mp 120e122 ꢀC.1HNMR(400 MHz,CDCl3):
d
¼8.16(s,1H),7.53(s,1H),
5.03 (m, 1H). 13C NMR (100 MHz, CDCl3):
d
¼136.6, 136.5, 133.4, 132.7,
7.33e7.24 (m, 6H), 7.17 (d, J¼8.6 Hz,1H), 7.02 (d, J¼1.9 Hz,1H), 5.10 (t,
J¼8.0 Hz, 1H), 4.99 (dd, J¼12.5, 8.0 Hz, 1H), 4.90 (dd, J¼12.5, 8.0 Hz,
128.8, 127.9, 127.6, 126.4, 126.3, 126.1, 126.0, 125.8, 122.7, 121.7, 120.0,
118.9,114.3, 111.4, 79.4, 41.6. MS m/z (relative intensity) 316 (Mþ, 31),
270 (29), 269 (100), 268 (30), 256 (65), 254 (49),149 (21),127 (20), 57
(33). HRMS calcd for C20H16O2N2 (Mþ), 316.1212; found: 316.1.
1H). 13C NMR (100 MHz, CDCl3):
127.8,125.8,123.0,121.6,114.2,113.4,113.1, 79.6, 41.5. MS m/z (relative
intensity) 346 (Mþ2, 26), 344 (Mþ, 27), 297 (100), 284 (54), 218 (88),
204 (27). HRMS calcd for C16H13BrN2O2 344.0160; found: 344.0155.
d
¼138.9, 135.3, 129.2, 128.1, 128.0,
4.7.9. 3-(2-Nitro-1-(thiophen-2-yl)ethyl)-1H-indole (9a). Solid, mp
92e94 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼8.12 (s, 1H), 7.52 (d,
4.7.16. 1,4-Bis(1-(1H-indol-3-yl)-2-nitroethyl)benzene (16a). Solid,
J¼8.0 Hz, 1H), 7.37 (d, J¼8.1 Hz, 1H), 7.25e7.19 (m, 2H), 7.11 (t,
J¼7.4 Hz, 2H), 6.99e6.93 (m, 2H), 5.45 (t, J¼7.9 Hz, 1H), 5.06e4.95
mp 191e193 ꢀC. 1H NMR (DMSO-d6, 400 MHz):
d
¼11.00 (br s, 2H),
7.46 (dd, J¼7.6, 5.6 Hz, 2H), 7.36e7.35 (m, 6H), 7.31 (d, J¼8.1 Hz, 2H),
(m, 2H). 13C NMR (100 MHz, CDCl3):
125.4, 125.1, 122.9, 122.2, 120.2, 119.0, 114.1, 111.7, 80.2, 37.1. MS m/z
(relative intensity) 274 (Mþ2, 3), 272 (Mþ, 42), 225 (100), 212 (72).
HRMS calcd for C14H12N2O2S (Mþ), 272.0619; found: 272.0614.
d
¼143.1, 136.6, 127.1, 125.9,
7.05e7.02 (m, 2H), 6.93e6.88 (m, 2H) 5.32e5.20 (m, 4H), 4.99e4.90
(m, 2H). 13C NMR (DMSO-d6, 100 MHz):
d
¼139.2, 136.1, 127.9, 126.0,
122.3, 121.3, 118.6, 118.3, 113.3, 111.5, 79.0, 40.2. MS m/z (relative
intensity) 454 (Mþ, 25), 374 (40), 216 (10), 187 (10), 143 (100), 131
(30). HRMS calcd for C26H22N4O4 (Mþ) 454.1641; found 454.1632.
4.7.10. 3-(1-(Furan-2-yl)-2-nitroethyl)-1H-indole (10a). Solid, mp
69e71 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼8.07 (s, 1H), 7.53 (d,
4.7.17. 1,4-Bis(1-(2-methyl-1H-indol-3-yl)-2-nitroethyl) benzene
J¼7.9 Hz, 1H), 7.35 (d, J¼1 Hz, 1H), 7.30 (d, J¼8.1 Hz, 1H), 7.21e7.17
(m, 1H), 7.11 (t, J¼7.4 Hz, 1H), 7.02 (d, J¼2.4 Hz, 1H), 6.28e6.27 (m,
1H), 6.13 (d, J¼3.2 Hz, 1H), 5.22 (dd, J¼8.1, 7.4 Hz, 1H), 5.02 (dd,
J¼12.5, 8.1 Hz, 1H), 4.87 (dd, J¼12.5, 7.4 Hz, 1H). 13C NMR (100 MHz,
(17a). Solid, mp 238e240 ꢀC. 1H NMR (DMSO-d6, 400 MHz):
d
¼10.9 (br s, 2H), 7.44 (d, J¼8.0 Hz, 2H), 7.30 (s, 4H), 7.22 (d,
J¼8.0 Hz, 2H), 6.95 (t, J¼7.6 Hz, 2H), 6.84 (t, J¼7.6 Hz, 2H) 5.47e5.42
(m, 2H) 5.25e5.31 (m, 2H), 4.97e5.10 (m, 2H), 2.39 (s, 6H). 13C NMR
CDCl3):
d
¼152.0, 142.2, 136.3, 125.3, 122.6, 120.1, 118.7, 111.7, 111.5,
(DMSO-d6, 100 MHz):
d
¼138.9, 135.5, 133.2, 127.6, 126.5, 120.3,
110.2, 107.4, 77.5, 35.7. MS m/z (relative intensity) 256 (Mþ, 32), 210
(22), 209 (100), 196 (84), 167 (23), 117 (16), 115 (12). HRMS calcd for
C14H12O3N2 (Mþ) 256.0848; found: 256.0846.
118.7, 118.5, 110.9, 108.2, 78.2, 40.2, 11.7. MS m/z (relative intensity)
482 (Mþ, 12), 422 (9), 374 (16), 216 (6), 187 (6), 143 (100), 129 (30).
HRMS calcd for C28H26N4O4 (Mþ) 482.1954; found 482.1949.
4.7.11. 2-(N-Methylindol-3-yl)-2-phenyl-1-nitroethane (11a). Solid,
4.7.18. 1,4-Bis(1-(5-methyl-1H-indol-3-yl)-2-nitroethyl) benzene
mp 94e96 ꢀC. 1H NMR (400 MHz, CDCl3):
d¼7.45 (d, J¼8.0 Hz, 1H),
(18a). Solid, mp 272e274 ꢀC. 1H NMR (400 MHz, CDCl3):
d
¼10.87
7.35e7.32 (m, 4H), 7.28e7.20 (m, 3H), 7.09e7.05 (m, 1H), 6.86 (s,
(s, 2H), 7.77 (S, 4H), 7.59 (d, J¼8 Hz, 2H), 7.35e7.24 (m, 2H), 7.20